Low Surface Energy Touch Screens, Coatings, and Methods

ABSTRACT

Substrates, surfaces, assemblies, kits, compositions, and methods are provided for forming touch screens and other appliance surfaces exhibiting good hydrophobicity, oleophobicity, and abrasion resistance. Methods are provided for increasing a population density of hydroxyl groups on a touch surface of a touch screen substrate without affecting the compressive strength of the back surface. The treated touch surface of the substrate can then be coated with a coating that includes an organo-metalic and/or silane, for example, a fluorosilane such as a perfluoropolyether alkoxysilane. A substrate can retain its compressive resistance to breakage by impact applied to the touch surface while minimizing any decrease in compressive strength against impact against the touch surface. Examples of such substrates include touch screens for mobile and desktop electronic devices, components of 3D display devices, and components for electrowetting display devices.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.14/687,475, filed Apr. 15, 2015, now U.S. Pat. No. 9,249,050 B2, whichin-turn is a Continuation of U.S. patent application Ser. No.13/544,360, filed Jul. 9, 2012, now U.S. Pat. No. 9,035,082 B2, whichin-turn claims priority to U.S. Provisional Patent Application No.61/545,556 filed Oct. 10, 2011, all of which are incorporated herein intheir entireties by reference.

FIELD

The present teachings relate to substrate coatings that increasehydrophobicity, oleophobicity, and abrasion resistance.

BACKGROUND

The explosive growth of both portable and desktop touch screen deviceshas meant a heightened need to keep such surfaces clean. Use of a touchscreen device, by name, involves touching by a user's fingers. Any oils,moisture, or various other materials found on one's fingertips can betransferred to the surface of a touch screen device. Overtime, thesematerials can accumulate and deleteriously affect the functionality,viewability, and general appearance of the device. Existing coatingcompositions and/or methods have proved unsatisfactory in terms of cost,efficient use of materials, longevity and/or the ability to resistabrasion, water, cleaning agents and lipids.

Glass hardening has been used to strengthen touch screen substratesagainst breakage, scratching and abrasion. Conventional hardeningtechniques, however, result in glass surfaces having reduced populationdensities of hydroxyl groups that could be used for bonding with anorgano-metalic and/or silane coating material. Treating substrates toincrease hydroxyl group population densities destroys or removessurface-compression elements, such as large atoms or ions, and strengthgains from pre-hardening procedures are lost. Accordingly, there existsa need for better pre-hardened glass substrates for touch screens, andfor coating methods and compositions for forming touch screen surfaces.

SUMMARY

According to various embodiments of the present teachings, apre-hardened glass substrate is provided that comprises a treated frontsurface having a first exposed hydroxyl population density and a backsurface having a second exposed hydroxyl population density, wherein thefirst exposed hydroxyl population density is greater than the secondexposed hydroxyl population density. The pre-hardened glass substratecan retain atoms or ions, such as potassium, hardened into the backsurface while providing a touch surface that can be optimally coatedwith an organo-metalic and/or silane-containing coating material. Thecoating material may also comprise metals, metal compounds, otherelements or their compounds, and combinations thereof. As a result, atouch screen can be formed from the pre-hardened glass substrate, whichhas a touch surface that exhibits improved longevity, wear resistance,lubricity, oleophobicity, and hydrophobicity, without sacrificing thebenefits enured to the back surface from a glass hardening procedure.Compressive strength gains from a pre-hardening procedure are notdestroyed on the back surface while the touch surface provides anincreased population density of reactive sites for organo-metalic and/orsilane treatment. Methods and compositions for treating suchpre-hardened glass substrates, for further treating such substrates withorgano-metalic compounds, co-agents and silanes are also provided. Inother embodiments, surface groups naturally present or absent on varioussubstrates may be increased or added in addition to hydroxyl groups.

According to various embodiments, methods more generally for treatingsubstrates, pre-hardened substrates, flexible substrates, rigidsubstrates, polymeric substrate, glass substrates, metalic substrates,inorganic substrates, and the like, are provided.

According to various embodiments of the present teachings, an assemblyfor quantitatively treating a surface is provided. The assembly cancomprise a first adhesive surface having a first area. The assembly cancomprise a second surface having a second area, facing and spacedsubstantially uniformly apart by a distance from the first adhesivesurface. The second surface may be adhesive or non-adhesive. A capillaryvolume can be defined by and between the first adhesive surface and thesecond surface. A first fluid can be loaded into the capillary. Thefirst fluid can comprise a chemical composition or molecule having anumber of adhesion functional groups. The functional groups, whendisposed as a monolayer, can make up a third area substantially equal toa first fraction of the first area. The fraction can be one, more thanone, or less than one.

According to various embodiments of the present teachings, a method ofcoating substrate surface is provided. The substrate can be rigid,flexible, glass, plastic, metal, inorganic, a combination thereof, orthe like. A fluid comprising molecules comprising adhesion functionalgroups is applied to a first adhesive substrate surface having a firstarea. A second substrate surface having a second area is placed on firstadhesive substrate surface. The second substrate surface may be adhesiveor non-adhesive. The second substrate may be non-adhesive to theadhesion functional groups, may be repellant to the adhesion functionalgroups, yet may have an affinity for a part of the molecule which is notadhesive. A substantially uniform layer of the fluid can then be formedbetween and in contact with the first adhesive substrate surface and thesecond substrate surface. The molecules can then be caused to adhere tothe first and/or second substrate surfaces. The amount of the moleculescomprising adhesion functional groups that can be applied can be suchthat, when disposed in a monolayer, the adhesion functional groups havea third area substantially equal to a fraction of the first and secondareas. The fraction can be one, more than one, or less than one. Thefirst and second substrate surfaces can then be separated after a periodof time.

According to various embodiments of the present teachings, a method ofmanufacturing a treated substrate is provided. A substrate can beprovided having a first surface comprising exposed hydroxyl groups and asecond surface comprising exposed hydroxyl groups. The substrate can berigid, flexible, glass, plastic, metalic, inorganic, a combinationthereof, or the like. The first surface can be treated to increase thepopulation density of exposed hydroxyl groups and form a treatedsurface, without treating the second surface. The method can provide ahigher population density of exposed hydroxyl groups on the firstsurface than on the second surface, wherein the treated substrateretains its resistance to breakage by impact or pressure applied to thefirst surface because surface-compressive elements in the second surfacehave not been removed or destroyed.

According to various embodiments of the present teachings, a method oftreating a substrate comprising a surface having exposed hydroxyl groupsis provided. The method can comprise contacting a surface with acomposition comprising components A and B combined together, acomposition comprising A followed by a composition comprising B, or acomposition comprising B followed by a composition comprising A, whereincomponent A is at least one fluorochemical polyether alkoxy or chloroorgano-metalic and/or silane compound of formula (1):

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. Component Bcan comprise tetraalkoxysilane, in an amount of 8% by weight or lessbased on the total weight of components A and B, when combined together.In other embodiments, Component B can be a metal or element comprising 3or more hydrolyzable groups, for example, a tetraalkoxysilane, and mayfurther comprise any suitable additives. The composition can furthercomprise forming a coating from the composition on the surface bycausing components A and B to undergo a substantially completecondensation reaction.

According to various embodiments of the present teachings, a compositioncomprising the reaction product obtained after a substantially completecondensation reaction of components A and B is provided. Component A cancomprise at least one fluorochemical polyether alkoxy or chloroorgano-metalic and/or silane compound of formula (1):

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. Component Bcan comprise a tetraalkoxysilane in an amount of 8% by weight or lessbased on the total weight of components A and B, when combined together.In other embodiments, Component B can be a metal or element comprising 3or more hydrolyzable groups, for example, a tetraalkoxysilane, and mayfurther comprise any suitable additives, such as additives comprising areactive functionality.

According to various embodiments of the present teachings, a kitequipped for substrate coating is provided comprising a first containerand a second container packaged in a third container. The firstcontainer can comprise at least one fluorochemical polyether alkoxy orchloro organo-metalic and/or silane compound of the formula (1):

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. A secondcontainer comprises a tetraalkoxysilane and/or one or more metals orelements comprising hydrolyzable groups, and may further comprise anysuitable additives. In some embodiments, the amount of tetraalkoxysilanecan be 8% by weight or less based on the total weight of the combinedcontents of the first container and second container.

The present teachings also provide a touch screen that exhibits a watercontact angle of 100° or more after 3000 double rubs with 0000 steelwool at a pressure of 2.5 grams per square millimeter.

BRIEF DESCRIPTION OF THE DRAWINGS

A better understanding of the features and advantages of the presentdisclosure will be obtained by reference to the accompanying drawings,which are intended to illustrate, not limit, the present teachings.

FIG. 1 is a schematic representation of substrate surfaces comprisingfree hydroxyl groups in accordance with various embodiments of thepresent teachings and comparing the population density of hydroxylgroups to the density on a glass surface.

FIG. 2 is a perspective view of an assembly for manufacturing treatedand coated substrate surfaces in accordance with various embodiments ofthe present teachings.

FIG. 3 is a flow chart illustrating a method of coating substratesurfaces in accordance with various embodiments of the presentteachings.

FIG. 4 is a flow chart illustrating a method of manufacturing a treatedsubstrate in accordance with various embodiments of the presentteachings.

FIG. 5 is a flow chart illustrating a method of treating a substrate inaccordance with various embodiments of the present teachings.

FIG. 6 is a partial cutaway view of a kit in accordance with variousembodiments of the present teachings.

DETAILED DESCRIPTION OF THE DISCLOSURE

According to various embodiments of the present teachings, aperfluoropolyether silane is provided, of the formula:

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)

wherein R_(f) represents a pendant polyfluoropolyether, R¹ represents aC₁-C₈ alkyl group, Y represents a hydrolysable group independentlyselected from a chloro group, an alkoxy group, an acyloxy group, and anaryloxy group, each R independently represents hydrogen or an alkylgroup of 1 to 4 carbon atoms, z is 2, 3, or 4, and each x isindependently 0 or 1. The pendant perfluoropolyether can be any type ofperfluoropolyether, for example, a K type or Y type perfluoropolyether.The pendant perfluoropolyether can have a molecular weight of from about500 to about 10,000 amu, for example, from about 2000 to about 5000 amu.The hydrolysable group can comprise a chloro group, a methoxy group, anethoxy group, a combination thereof, or the like. A compositioncomprising the perfluoropolyether silane and one or more additives isalso provided. The additives can comprise, for example, a tetraalkoxysilane, a polysilane, a polyorganometalic compound, a dipodal silane, adipodal organometalic compound, a combination thereof, and the like. Thecomposition can instead, or additionally, comprise a fluorinated solventas an additive. According to various embodiments, articles, for example,display devices, can be coated with the perfluoropolyether silane. Insome cases, the article can comprise a smooth surface that is coated, atleast in part, by the perfluoropolyether silane. In some cases, thearticle can comprise a rough surface that is coated, at least in part,by the perfluoropolyether silane, and the rough surface can have arepeating or random topography, a relief, an impression, a texture, apattern, a design, a feature, a combination thereof, or the like. Thearticle can comprise a touch screen that is coated, at least in part, bythe perfluoropolyether silane, or a 3D imaging screen that is coated, atleast in part, by the perfluoropolyether silane, or an electrowettingdisplay screen that is coated, at least in part, by theperfluoropolyether silane.

According to various embodiments of the present teachings, aperfluoropolyether silane is provided of the formula:

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)

wherein R_(f) represents a pendant polyfluoropolyether, Q represents adivalent linking group, R¹ represents a C₁-C₈ alkyl group, Y representsa hydrolysable group independently selected from a chloro group, analkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. The pendantperfluoropolyether can be any type of perfluoropolyether, for example, aK type or Y type perfluoropolyether. The pendant perfluoropolyether canhave a molecular weight of from about 500 to about 10,000 amu, forexample, from about 2000 and about 5000 amu. The hydrolysable group cancomprise a chloro group, a methoxy group, an ethoxy group, a combinationthereof, or the like. A composition comprising the perfluoropolyethersilane and one or more additives is also provided. The additives cancomprise, for example, a tetraalkoxy silane, a polysilane, apolyorganometalic compound, a dipodal silane, a dipodal organometaliccompound, a combination thereof, and the like. The composition caninstead, or additionally, comprise a fluorinated solvent as an additive.In some cases, the perfluoropolyether silane can comprise the reactionproduct of a pendant perfluoropolyether vinyl ether and Cl₃SiH. Themethods can comprise reacting a pendant perfluoropolyether vinyl etherand Cl₃SiH together. In some cases, the perfluoropolyether silanecomprises the reaction product of a pendant perfluoropolyethertrichlorosilane and one or more alcohols selected from methanol,ethanol, and propanol, and the methods herein can comprise reactingthese reactants together. According to various embodiments, articles,for example, display devices, can be coated with the perfluoropolyethersilane. In some cases, the article can comprise a smooth surface that iscoated, at least in part, by the perfluoropolyether silane. In somecases, the article can comprise a rough surface that is coated, at leastin part, by the perfluoropolyether silane, and the rough surface canhave a repeating or random topography, a relief, an impression, atexture, a pattern, a design, a feature, a combination thereof, or thelike. The article can comprise a touch screen that is coated, at leastin part, by the perfluoropolyether silane, or a 3D imaging screen thatis coated, at least in part, by the perfluoropolyether silane, or anelectrowetting display screen that is coated, at least in part, by theperfluoropolyether silane.

According to various embodiments of the present teachings, apre-hardened glass substrate is provided that comprises a first surfacehaving a first exposed hydroxyl population density and a post-treatedsecond surface having a second exposed hydroxyl population density. Thefirst exposed hydroxyl population density can be less than the secondexposed hydroxyl population density and the second surface can be coatedto form a touch surface. The pre-hardened glass substrate can retain itscompressive resistance to breakage by impact or pressure applied to thesecond surface while minimizing any decrease in tensile strength of thefirst surface.

The second exposed hydroxyl population density can have a range ofdensities, for example, from about 2.0 to about 5.0, from about 2.0 toabout 2.5, or about 2.2 hydroxyl groups per square nanometer. In someembodiments, the second exposed hydroxyl population density has adensity greater than about 2.2 hydroxyl groups per square nanometer. Insome embodiments, the first exposed hydroxyl population density is lessthan about 1.8 hydroxyl groups per square nanometer. The second exposedhydroxyl population density can be greater than the first exposedhydroxyl population density by about 0.1 to about 3.2, from about 0.25to about 2.5, or about 0.4 hydroxyl groups per square nanometer.According to the present teachings, the second exposed hydroxylpopulation density can be equivalent to the amount of a firstorgano-metalic and/or silane that will be used to coat the surface, suchthat each first organo-metalic and/or silane molecule will substantiallyonly attach to a single hydroxyl group and not to a neighboringorgano-metalic and/or silane. Such stoichiometry forms a coating that isnot a two-dimensional network of molecules. Adjacent firstorgano-metalic and/or silanes, once bonded to the surface, can becrosslinked to one another simultaneously or subsequently by a secondorgano-metalic and/or silane. The second organo-metalic and/or silanecan be the same as the first.

The post-treated second surface can have been treated by any suitableprocess to selectively increase the second exposed hydroxyl populationdensity. In some embodiments, the process to selectively increase thesecond exposed hydroxyl population density comprises a plasma process,including a plasma jet process, or an abrasive precess. The process toselectively increase the second exposed hydroxyl population density cancomprise exposure to steam, ammonia, hydrogen peroxide, an acid, a base,fluorine, a halogen compound, an oxidizing agent, a reducing agent, or acombination thereof. In some examples, the touch surface can be treatedto increase the hydroxyl group population density by contacting thetouch surface with a solution comprising from about 3% by volume toabout 30% by volume ammonium hydroxide, from about 3% by volume to about30% by volume hydrogen peroxide, and from about 40% by volume to about94% by volume water. Another exemplary treating solution that can beused comprises from about 3% by volume to about 30% by volumeconcentrated sulfuric acid, from about 3% by volume to about 30% byvolume hydrogen peroxide, and from about 40% by volume to about 94% byvolume water. Another exemplary treating solution that can be usedcomprises from about 0.1% by weight to about 10% by weight ammoniumbifluoride, and from about 90% by weight to about 99% by weight water.Dilute solutions of aqueous hydrofluoric acid are also preferred, as areconcentrated solutions of sodium hydroxide. In other embodiments,surface groups naturally present or absent on various substrates may beincreased or added, in addition to hydroxyl groups, by the presentteachings.

After treating to increase hydroxyl group population density, thepost-treated second surface can be reacted with a touch screen coatingcomposition. In some embodiments, the post-treated second surface can bereacted with a first organo-metalic and/or silane, for example, amonoorgano-metalic and/or monosilane, a diorgano-metalic and/ordisilane, a triorgano-metalic and/or trisilane, a tetraorgano-metalicand/or tetrasilane, a polyorgano-metalic and/or polysilane, or acombination thereof, each comprising one, two, three, four or polyhydrolysable groups, respectively. For purposes of the presentteachings, chlorine will be considered a hydrolysable group. Silane andother organo-metalic groups can form from one to about four hydrolyzablelinkages, by way of example, a disilane can have from 2 to about 6linkages, and a tetrasilane can have from 4 to about 12 hydrolyzablelinkages. In some embodiments, the post-treated second surface can bereacted with at least a second organo-metalic and/or silane. The firstorgano-metalic and/or silane and/or the second organo-metalic and/orsilane can comprise a fluorinated organo-metalic and/or silane, forexample, a perfluorinated organo-metalic and/or silane. Theorgano-metalic and/or silane can be applied in the presence of ananhydride. In some embodiments, the anhydride can comprise a fluorinatedanhydride. The fluorinated organo-metalic and/or silane can comprise aperfluoropolyether. The fluorinated organo-metalic and/or silane cancomprise a polyorgano-metalic and/or silane comprising two or moreorgano-metalic and/or silane groups. In some embodiments, thepost-treated second surface is substantially covered by a layer of afluorinated solution, for example, containing an amount oforgano-metalic and/or silane sufficient to form a monomolecular layer ormore of organo-metalic and/or silane.

The post-treated second surface, or touch surface, can be reacted withany suitable number of organo-metalic and/or silane groups per squarenanometer to form single or multiple layers. A continuous monolayer oforgano-metalic and/or silane groups can be formed from about 6 to about10 groups per square nanometer. For example, to form a monolayer, thepost-treated second surface can be reacted with a quantity of firstorgano-metalic and/or silane groups at from about 1 group to about 2groups, and then subsequently reacted with a quantity of secondorgano-metalic and/or silane groups at from about 4 groups to about 9groups. The post-treated second surface can be exposed to a quantity oforgano-metalic and/or silane groups, which, when disposed as amonolayer, would cover an area substantially equal to a fraction ormultiple of the area of the second surface or a selected portionthereof. In some embodiments, the post-treated second surface has beenreacted with sufficient hydrolyzable organo-metalic material, forexample, tetra-hydrolyzable silicon, such as tetraethoxysilane, or acombination of organo-metalic materials to form at least one or moremonolayer(s) of silicate or silicate composite, and simultaneously orsecondarily exposed to a quantity of second organo-metalic and/or silanemolecules, which, when disposed as a monolayer, would cover an areasubstantially equal to the area of the second surface or a selectedportion thereof. The quantity of first organo-metalic and/or silanemolecules and/or quantity of second organo-metalic and/or silanemolecules can comprise perfluoropolyether organo-metalics and/orsilanes. The perfluoropolyether organo-metalic and/or silanes can have amolecular weight of between from about 500 and about 10,000. In someembodiments, the quantity of a first organo-metalic and/or silane isabout 2 molecules per square nanometer, and the quantity of a secondorgano-metalic and/or silane is from about 2 to about 7 molecules persquare nanometer. The post-treated second surface can be first reactedwith a quantity of organo-metalic and/or silane groups of apolyorgano-metalic and/or silane having organo-metalic and/or silanefunctional adhesive groups substantially equalling the number ofhydroxyl groups on the second surface, and then secondarily exposed to aquantity of second organo-metalic and/or silane molecules, comprisingmonofunctional organo-metalics and/or silanes, which, when disposed as amonolayer, would cover an area substantially equal to a remaining areaof the second surface. In other embodiments, the second fluid maycomprise adhesive functional groups that are different from the firstadhesive functional groups, and the molecules comprised in the first orprevious fluid may comprise functional groups which would be selectivelyadhesive to molecules comprising the second or previous fluid. Such acombination of differing functional groups may be drawn from any of thereactive chemical groups which are well know in the art, for example,nucleic acid base pairs, enzymes, epoxies, amines, alcohols,isocyanates, vinyls, or (meth)acrylics, to name a few. In someembodiments, the second or subsequent molecules may be crosslinked byadditional functional adhesive groups or adhesive pairs of groups drawnfrom a similar list.

The post-treated second surface can be a hydrophobic and/or oleophobicsurface useful as a touch surface for a touch-controlled electronicdevice. In some embodiments, the touch-controlled electronic devicefurther comprises a mechanism for polarizing or directing light toproduce 3D images. In various embodiments, the coated surface may bepart of an article or an appliance, such as a display device.

According to various embodiments of the present teachings, an assemblyfor quantitatively treating a surface is provided. The assembly cancomprise a first surface having a first area. The assembly can comprisea second surface having a second area, facing and spaced substantiallyuniformly apart from the first surface, by a distance. The firstsurface, the second surface, or both surfaces may be adhesive to anadhesion functional group. The first and second surfaces may bepositioned together such that a capillary volume can be defined by andbetween the first surface and the second surface. The assembly cancomprise a first fluid within the capillary volume, for example, to fillthe capillary volume. The fluid may be dispensed onto the first orsecond substrate prior to positioning the surfaces to form thecapillary, or the fluid may be loaded into the volume after the surfacesare positioned to form the capillary. The fluid can comprise a chemicalcomposition or molecule having a number of adhesion functional groups.The adhesion groups, when disposed as a monolayer, can be of sufficientarea to cover a third area that is substantially equal to a firstfraction of the first area. The adhesive functional groups may beactivated by the presence or absence of a substance, a polarizingelectric field, electromagnetic excitation, heat, or combinationsthereof.

The adhesive properties of the first adhesive surface and the secondsurface can vary or be the same. In some embodiments, the second surfaceis not adhesive to the adhesion functional group. In some embodiments,the second surface is not adhesive to the adhesion functional group andfurther comprises means or devices for introducing the fluids. In someembodiments, the second surface is not adhesive to the adhesionfunctional group and comprises a flexible film or sheet. In someembodiments, where the second surface is not adhesive to the adhesionfunctional group, the second surface may be porous to atoms ormolecules, allowing transport into and out of the capillary volume, forexample, to molecules of water or a catalyst. In some embodiments, thesecond surface is adhesive to the adhesive functional group, the firstand second areas are essentially equal, and the third area is equal to afirst fraction of the combined first and second areas. The firstfraction can be any suitable fraction of the first area, for example,the first fraction can be from about ⅛ to about 10/8, or from about ⅕and about 12/10 of the first area. In some embodiments, the firstfraction is less than or equal to about 1. In some embodiments the firstfraction can be a multiple of about 1. In some embodiments, the firstfraction can be substantially greater than one. The assembly cancomprise a device for introducing and/or withdrawing the first fluidand/or any additional fluid. The capillary can comprise one or morespacers. The spacers may be free in the fluid, introduced between thesurfaces, or attached to one or both of the first and second surfaces.The spacers may be solid, liquid or gas, or a combination thereof. Thefirst and second surfaces may be spaced substantially uniformly apartbecause of a balance between capillary forces and the fluid viscosity ora balance between gravity and electromagnetic forces. The first and/orsecond adhesive surface can comprise glass, and the adhesion functionalgroup can be any chemically reactive group well know in the art, forexample an organo-metalic group, such as a silane group, or acombinations thereof. The chemical composition or molecule can comprisea perfluoropolyether. The distance between the first adhesive surfaceand the second surface can be any appropriate distance. For example, thedistance can be less than about 5 mm, less than about 1 mm, less thanabout 100 μm, less than about 25 μm, from about 1 mm to about 10 nm,from about 100 μm to about 25 nm, or from about 30 nm to about 100 nm.

According to various embodiments of the present teachings, a method ofcoating substrate surfaces is provided. A fluid comprising moleculescomprising adhesion functional groups is applied to a first substratesurface having a first area. A second substrate surface having a secondarea is placed on the first substrate surface. A substantially uniformlayer of the fluid is formed between the first and second substratesurfaces. The first substrate surface and/or the second substratesurface may be adhesive to the adhesive functional groups. The moleculesare adhered or caused to adhere to the adhesive substrate surface. Themolecules comprising adhesive functional groups in the fluid can have aconcentration such that when the functional groups are disposed in amonolayer they have a third area substantially equal to a fraction ofthe first and/or second areas. The first and second substrate surfacescan then be separated after a time, whereafter a stage of an adhesionhas occurred. In some embodiments, at least a second fluid having aconcentration of molecules having adhesive functional groups capable ofadhering to the remaining adhesive substrate surface(s) and/or toadhesive groups comprised in the first fluid is applied. In someembodiments, the adhesive functional groups of the second fluid can bethe same as those of the first or a previous fluid. At least one spacercan be positioned or located between the first and second adhesivesubstrate surfaces. In some embodiments, the at least one spacer isattached to one or both adhesive substrate surfaces, or is present inthe fluids. The method can comprise collecting one or more of the fluidsfor reuse. In some embodiments, at least one of the adhesive substratesurfaces is a touch screen surface, an appliance, or a display device.

According to various embodiments of the present teachings, a method ofmanufacturing a treated substrate is provided. A substrate can beprovided having a first surface comprising exposed hydroxyl groups and asecond surface comprising exposed hydroxyl groups. The first surface canbe treated to increase the population density of exposed hydroxyl groupsand form a treated surface without treating the second surface toincrease the population density of exposed hydroxyl groups. The methodcan provide a higher population density of exposed hydroxyl groups onthe first surface than on the second surface, wherein the treatedsubstrate retains its compressive resistance to breakage by impactapplied to the first surface while minimizing any decrease in tensilestrength of the second surface. In some embodiments, the substrate usedin the method comprises a glass material. A glass material can behardened prior to the treating. In some embodiments, the glass materialis embedded with one or more kinds of large atoms or ions, such aspotassium ions, to place the substrate surfaces under compression,increasing resistance to breakage. In some embodiments, the glasssurface is hardened by cooling the surfaces rapidly from a temperatureabove the Tg for the glass. The treating can comprise buffing ortreating with at least one of ammonia, hydrogen peroxide, an acid, abase, bleach, fluorine, hydrofluoric acid, halogen compounds, anoxidizing agent, a reducing agent, a plasma, steam, or a combinationthereof, or any of the solutions described herein or known to in the artfor such purpose.

The method of manufacturing a treated substrate can further compriseapplying one or more coating to the treated surface. A coatingcomposition can be applied to the treated surface, and the coatingcomposition can comprise a first organo-metalic and/or silane, forexample an alkoxy or chloro organo-metalic and/or silane compound. Insome embodiments, the first organo-metalic and/or silane compoundcomprises a first perfluoropolyether alkoxy or chloro organo-metalicand/or silane compound. The first perfluoropolyether organo-metalicand/or silane compound can have a molecular weight of from about 500 toabout 10,000 atomic units, from about 500 to about 4,000 atomic units,from about 1000 to about 2500 atomic units, or more than about 10,000atomic units. In some embodiments, the first organo-metalic and/orsilane is a fluoroalkyl organo-metalic and/or silane. In someembodiments, a tetra-hydrolyzable organo-metalic compound, for example,tetraethoxysilane, is applied to the treated surface. In someembodiments, the tetra-hydrolyzable organo-metalic and/or silanecompound is applied to the treated surface at the same time theperfluoropolyether organo-metalic and/or silane compound is applied tothe treated surface, and they may be combined together prior toapplication to the treated surface. In some embodiments, thetetra-hydrolyzable organo-metalic is applied to the treated surfaceprior to applying the perfluoropolyether organo-metalic and/or silanecompound to the treated surface. In some embodiments the at least firstorgano-metalic and/or silane may be a chloro-organo-metalic or achlorosilane, for example, titanium tetrachloride or silicontetrachloride. In some embodiments, organo-metalic compounds that aremono-hydrolyzable, di-hydrolyzable, or tri-hydrolyzable, that is, havingone, two or three hydrolyzable linkages per atom, may be used as all orpart of the first or second coating treatments. In some embodiments theat least first organo-metalic and/or silane may be a monofunctionalorgano-metalic and/or silane, that is an organo-metalic and/or silanehaving, for example, one triethoxy organo-metalic and/or silane group.In some embodiments the at least first organo-metalic and/or silane maybe a di-functional organo-metalic and/or silane, that is anorgano-metalic and/or silane molecule having, for example, two triethoxyorgano-metalic and/or silane groups or, other embodiments, two trichloroorgano-metalic and/or silane groups. The coating composition may furthercomprise organo-metalic compounds. In some embodiments, atetra-hydrolyzable or tetrachloro organo-metalic and/or silane may becombined with one or more other silanes, organo-metalic compounds,organic compounds, elements, polyvalent elements, and compounds ofelements. In some preferred embodiments, a hydrolyzable organo-metalicand/or silane, such as tetraethoxysilane, and any other selectedingredients, additives or co-agents may be prepared as a sol-gel beforeapplication to a surface. In some preferred embodiments, the sol-gel mayinclude a fluorinated organo-metalic and/or silane, for example aperfluoropolyether organo-metalic and/or silane. In some embodiments,the coatings and application methods of the present teachings may beapplied to surfaces which have not been treated to increase the hydroxylpopulation density.

The method of manufacturing the treated and/or coated substrate canfurther comprise installing the treated and/or coated substrate in anappliance, a touch screen, a 3D device, an electrowetting displaydevice, a combination thereof, and the like. A treated and/or coatedsubstrate manufactured according to the present methods is alsoprovided. The treated and/or coated first surface of the substrate canbe a hydrophobic and/or oleophobic surface, for example, useful as atouch surface for a touch-controlled electronic device.

According to various embodiments of the present teachings, a method oftreating a substrate comprising a surface having exposed hydroxyl groupsis provided. The method can comprise contacting a surface with acomposition comprising components A and B combined together, acomposition comprising A followed by a composition comprising B, or acomposition comprising B followed by a composition comprising A, whereincomponent A is at least one fluorochemical polyether alkoxy or chloroorgano-metalic and/or silane compound of formula (1)

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms z is 2, 3, or 4, and each x is independently 0 or 1. Component Bcan comprise a tetraalkoxysilane in an amount of 8% by weight or lessbased on the total weight of components A and B, when combined together.In other embodiments, Component B can be a metal or element comprising 3or more hydrolyzable groups, for example, tetramethoxysilane, and mayfurther comprise any suitable additives, such as additives comprising areactive functionality. The method can further comprise forming acoating from the composition on the surface by causing components A andB to undergo a substantially complete condensation reaction.

The method of treating a substrate can be performed by varying orkeeping constant the timing of the mixing of components A and B or theindividual preparation of components A and B as separate components. Insome embodiments, components A and B are first mixed together beforethey contact the surface. In some embodiments, components A and B aremixed together and diluted in a solvent comprising a fluorosolvent toform a coating solution having a concentration of about 0.001% to about2%, or from about 0.02% to about 0.2% by weight or less of components Aand B combined, and the method comprises contacting the surface with thecoating solution. In some embodiments, components A and B are mixedtogether and diluted in a solvent comprising a fluorosolvent to form acoating solution having a concentration of about 0.02% to about 0.05% byweight or less of components A and B combined. The fluorosolvent cancomprise a fluorochlorosolvent. In some embodiments, the surface isfirst contacted with component B and then with component A, either orboth of which may be diluted with a solvent. In some embodiments, thesurface is first contacted with component A and then with component B,either or both of which may be diluted with a solvent. In someembodiments, the surface is first contacted with a diluted solution ofcomponent B in a solvent comprising a fluorosolvent and thensubsequently contacted with a diluted solution of component A in asolvent comprising a fluorosolvent. In some embodiments, the surface isfirst contacted with a diluted solution of component A in a solventcomprising a fluorosolvent and then subsequently contacted with adiluted solution of component B in a solvent comprising a fluorosolvent.The solvent may further comprise water, organic solvents, anhydrides,initiators, catalysts, and acid or base catalysts. In some embodiments,the solvent may further comprise an fluorinated anhydride. In someembodiments, the molar amount of water may equal or exceed the molaramount of hydrolyzable groups comprised in the organo-metalic and/orsilane molecule. In some embodiments, the solvent pH may be adjusted toa pH which promotes dense organo-metalic and/or silane condensationhaving a preferred thickness, for example, in a pH range of betweenabout 9 and about 12 and a thickness of between about 100 nm and about 1nm. The method of treating a substrate can be performed wherein thesurface comprises exposed hydroxyl groups and the method furthercomprises treating the surface to increase the number of exposedhydroxyl groups before the surface is contacted with the composition.Component A can comprise a perfluoropolyether organo-metalic and/orsilane having any suitable weight average molecular weight, for examplefrom about 250 to about 10,000, from about 500 to about 5000, or fromabout 1,000 to about 2,500 Daltons. In some embodiments, theperfluoropolyether may be coupled to one or more chloro organo-metalicand/or silanes and/or alkoxy organo-metalic and/or silanes. Theperfluoropolyether may be a pendant organo-metalic and/or silane. Insome embodiments the perfluoropolyether organo-metalic and/or silane maybe the silyl ether, for example, the derivative of a PFPE-Z and/or aPFPE-M perfluoropolyether. In some embodiments, the surface treated inthe method comprises a touch screen surface, a 3D device, anelectrowetting display device, a combination thereof, and the like.

According to various embodiments of the present teachings, a compositioncomprising the reaction product obtained after a substantially completecondensation reaction of components A and B is provided. Component A cancomprise at least one fluorochemical polyether chloro organo-metalicand/or silane or alkoxy organo-metalic and/or silane compound of formula(1):

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. Component Bcan comprise a tetraalkoxysilane in an amount of 8% by weight or lessbased on the total weight of components A and B, when combined together.In other embodiments, Component B can be a metal or element comprising 3or more hydrolyzable groups, for example, a tetraaryloxysilane, and mayfurther comprise any suitable additives, such as additives comprisingmore than one chemical or reactive functionality. In some embodiments,component B is present in an amount of from about 1% by weight to about7% by weight based on the total weight of components A and B combined.Component A can comprise a perfluoropolyether organo-metalic and/orsilane, for example an alkoxy organo-metalic and/or silane or chloroorgano-metalic and/or silane, having any suitable number averagemolecular weight, for example from about 250 to about 10,000, from about500 to about 5000, or from about 1,000 to about 2500 Daltons. In someembodiments, the composition is coated on a surface of a substrate as acoating, wherein the coating has a thickness of from about 2.0 to about4.0 nanometers, or less than 4.0 nanometers. In some embodiments, thecomposition is coated on a surface of a substrate as a coating, whereinthe coating comprises two layers, and the layer comprising component Bhas a thickness of from about 1 nanometer to about 100 nanometers. Thecoating can comprise a mono-molecular layer of the reaction product, themonomolecular layer continuous with the underlying substrate so as toconstitute a monolithic surface comprising exposed fluorine compounds.In some embodiments, the composition is in the form of a coating on atouch screen surface, a 3D device, an electrowetting display device, acombination thereof, and the like. In some embodiments, the coating issubstantially in the form of a monolayer.

According to various embodiments of the present teachings, a kitequipped for substrate coating is provided comprising a first containerand a second container packaged in a third container. The firstcontainer comprises at least one fluorochemical polyether organo-metalicand/or silane compound of formula (1):

R_(f)-[Q-CR₂Si(Y)₃-x(R¹)_(x)]_(z)  (1)

wherein R_(f) represents a polyfluoropolyether segment, Q represents anorganic divalent linking group, R¹ represents a C₁-C₈ alkyl group, Yrepresents a hydrolysable group independently selected from a chlorogroup, an alkoxy group, an acyloxy group, and an aryloxy group, each Rindependently represents hydrogen or an alkyl group of 1 to 4 carbonatoms, z is 2, 3, or 4, and each x is independently 0 or 1. A secondcontainer comprises a tetraalkoxysilane, in an amount of 8% by weight orless based on the total weight of the combined contents of the firstcontainer and second container and/or a metal or element comprising 3 ormore hydrolyzable groups and may further comprise any suitableadditives. The contents of the first container can comprise aperfluoropolyether organo-metalic and/or silane, for example an alkoxyorgano-metalic and/or silane or a chloro organo-metalic and/or silane,having any suitable number average molecular weight, for example fromabout 250 to about 10,000, from about 500 to about 5000, or from about1,000 to about 2500 Daltons. In some embodiments, the contents of thesecond container are present in an amount of from about 0.05% by weightto about 7% by weight based on the total weight of the contents of thefirst and second containers.

The compositions, coatings, polymers, chemicals, solvents, substrates,surfaces, assemblies, kits, and methods as described, for example, inthe following publications can be used in conjunction with variousembodiments of the present teachings: U.S. Pat. No. 4,861,667; U.S. Pat.No. 6,270,903 B1; U.S. Pat. No. 6,447,919 B1; U.S. Pat. No. 6,495,624B1; U.S. Pat. No. 6,767,587 B1; U.S. Pat. No. 7,268,179 B2; U.S. Pat.No. 7,579,056 B2; U.S. Pat. No. 7,781,027 B2; U.S. Pat. No. 7,803,894B2; U.S. Pat. No. 7,824,043 B2; U.S. Pat. No. 7,871,675 B2; U.S. Pat.No. 7,999,013 B2; U.S. Patent Application Publication Nos. US2001/0019773 A1; US 2003/0124361 A1; US 2003/0138643 A1; US 2003/0139620A1; US 2004/0091720 A1; US 2004/0092675 A1; US 2006/0010537 A1; US2008/0220264 A1; US 2009/0197048 A1; US 2009/0326146 A1; US 2010/0015344A1; US 2010/0053547 A1; US 2010/0210769 A1; US 2010/0239823 A1; US2010/0285275 A1; US 2010/0304086 A1; US 2010/0324205 A1; and US2011/0003098 A1, which are incorporated herein in their entireties byreference.

With reference now to the drawings, FIG. 1 is a schematic representationof substrate surfaces comprising free hydroxyl groups 50 in accordancewith various embodiments of the present teachings. Hydroxyl (OH) groupsare randomly located on quartz and glass, typically about 5 groups and 2groups per square nanometer, respectively. The outer circle of each freehydroxyl group 50 corresponds to the attachment zone for a single OHgroup with the understanding that the hydroxyl groups are not mobile.Tetra-hydrolyzable organo-metalic and/or silane andPFPE-tri-hydrolyzable organo-metalic and/or silane groups can be bondedonto the surface. As can be seen, the quartz surface provides a muchgreater population density of hydroxyl groups than does the glasssurface, for example, 5 hydroxyl groups per square nanometer. Theprobability of PFPE diorgano-metalic and/or disilane molecules, that is,having two organo-metalic or silane groups, being bonded at both ends isunlikely above stoichiometric levels pairing surface hydroxyl groupswith silane or organo-metalic groups. A condensed layer oftetra-hydrolyzable silane can convert the glass surface to a quartz-likesurface, providing up to about 5 hydroxyl groups per square nanometer.The addition of other organo-metalic compounds to the surface canprovide hydroxyl groups or other desirable properties.

FIG. 2 is a perspective view of an assembly 120 for manufacturingtreated and coated substrate surfaces in accordance with variousembodiments of the present teachings. Assembly 120 can be constructedfrom a first substrate 122 and a second substrate 124. First substrate122 can have a first inwardly facing surface 126. Second substrate 124can have a second inwardly facing surface 128. First and secondsubstrates 122, 124 can be separated from each other by a first spacer130 and a second spacer 132. The region between the first and secondinwardly facing surfaces 126, 128 can constitute a capillary volume 134capable of holding one or more fluids. The fluid to be loaded intocapillary volume 134 can comprise adhesive molecules capable of adheringto at least one of the first and second inwardly facing surfaces 126,128.

FIG. 3 is a flow chart for a method 220 of coating substrate surfaces inaccordance with various embodiments of the present teachings. In a step230, a fluid can be applied to a first adhesive surface. The fluid cancontain one or more kinds of molecules having adhesion groups. In step240, a second adhesive substrate can be placed on the covered firstadhesive surface. In a step 250, a substantially uniform layer of afluid between the first and second substrate surfaces can be formed. Themolecules can adhere to the first and second adhesive surfaces in step260. In step 270, the first and second adhesive surfaces can beseparated.

FIG. 4 is a flow chart for a method 320 of manufacturing a treatedsubstrate in accordance with various embodiments of the presentteachings. In a step 330, a substrate is provided having a first surfacecomprising exposed hydroxyl groups, and a second surface comprisinghydroxyl groups. The first surface can be treated in a step 340 toincrease the population density of exposed hydroxyl groups and form atreated surface, without treating the second surface.

FIG. 5 is a flow chart for a method 420 of treating a substrate inaccordance with various embodiments of the present teachings. In a step430, a surface is contacted with a composition comprising component Aand component B, wherein component A and component B are as describedherein. A coating is formed on the surface from the composition in astep 440 by causing components A and B to undergo a substantiallycomplete condensation reaction.

FIG. 6 is a cross-sectional, partial cutaway view of a kit 520 inaccordance with various embodiments of the present teachings. Kit 520can comprise a first container 522 containing first contents 524. Firstcontents 524 can comprise component A as described herein. Kit 520 alsocomprises a second container 526 containing second contents 528. Secondcontents 528 can comprise component B as described above. Firstcontainer 522 and second container 526 can each independently be a vial,a tube, a jar, an ampule, a box, a dish, or the like. First container522 and second container 526 can be packaged together in a thirdcontainer 530, for example, a box. The kit can further compriseinstructions for use of first contents 524 and second contents 528 tocoat a surface.

According to various embodiments of the present teachings, less, ratherthan more, of a coating is used to coat a substrate and form in atwo-dimensional network. According to various embodiments of the presentteachings, an exact amount of a coating component is used to coat anarea of a substrate and form in a two-dimensional network. According tovarious embodiments of the present teachings, exact amounts of coatingcomponents are used to coat an area of a substrate and form in a layeredthree-dimensional network. Substrates that can be used include glassthat has been immersed in a bath of molten minerals, for example salts,to exchange sodium ions for potassium ions, putting the surface undercompression. In some embodiments, substrates that can be used includeglass that has been heated above its Tg and then the surface cooledquickly, putting the surface under compression. In some embodiments,substrates that can be used include glass that has been strengthened orhardened by other means well known in the art. The subsequent coatingtreatment can be applied to one side of the resulting glass substratebut not the other. For an optimal polyorgano-metalic and/or silanecoating treatment, the number of exposed hydroxyl groups can besubstantially the same as the number of reactive groups intended toreact with the surface. For an optimal mono-organo-metalic and/or silanecoating treatment, the number of exposed hydroxyl groups can be lessthan the number of reactive groups intended to react with the surface,for example, about 4 to 5 times less, in other words, the number ofreactive groups can be 4-5 times greater than the number of hydroxylgroups in order to form a continuous monolayer. Increasing the exposedhydroxyl group population density increases the adhesion of a network oforgano-metalic and/or silanes. Increasing the exposed hydroxyl grouppopulation density can be particularly useful when a surface has beenhardened, for example, heated above 500° C., which can reduce thedensity of available hydroxyl groups for long periods of time. Glass,generally, has a density of about 2.2 hydroxyl groups per squarenanometer, high temperature treated glass often has a density of about1.7 hydroxyl groups per square nanometer, and quartz generally has adensity of about 5 hydroxyl groups per square nanometer.

In some embodiments, the substrate is a touch screen and the surfaceenhanced in exposed hydroxyl group population density is the side(surface) that will be coated and subsequently “touched” by a user. Invarious embodiments, the substrate is an appliance or display device,for example a 3D and/or electrowetting display device. The chemicalcoating can be applied to the touch surface using any means, forexample, spraying, spinning, dipping, brushing, fogging, vacuumdeposition, or the like. Tin oxide and circuitry, if present on the backsurface, can remain unaffected during that process. Other circuitry suchas piezoelectric sensors can also remain unaffected by the coatingprocess on the touch surface. Glass is strong under compression and weakunder tension, and when impacted, the touch surface is generally undercompression while the back surface may become under tension. Hardened orstrengthened glass surfaces are pre-compressed, such that impacts areless likely to put the back surface under tension, therefore it isbeneficial to preserve compressive treatments to the back side of atouch surface. The population density of hydroxyl groups can generallybe increased, for example, to about 2.0 per square nanometer, to about2.5 per square nanometer, or greater. The process of increasing hydroxylgroup concentration on the touch surface can start with unhardened glassor a glass substrate that is hardened on one or both sides. The processof increasing hydroxyl group concentration on a touch surface may removecompressive elements or compressed layers at the surface withoutdisturbing compressive elements or compressed layers at the backsurface. The treated side can become more quartz-like than glass-like,if the treated side is subsequently coated with silicate. In someembodiments, the composition used for treatment comprises 10% to 20% byweight ammonium hydroxide, 60% to 80% by weight water, and 10% to 20% byweight hydrogen peroxide, based on the total weight of the composition.In some embodiments, the composition used for treatment comprises 10% to20% by weight sulfuric acid, 60% to 80% by weight water, and 10% to 20%by weight hydrogen peroxide, based on the total weight of thecomposition. The resulting hydroxyl group content of the treated surfacecan be determined using the techniques of X. M. Liu, J. L. Thomason,about F. R. Jones from the University of Sheffield and the University ofStrathclyde. Any type of glass can be used, for example, GORILLA® Glassavailable from Corning, Inc. of Corning, N.Y. B270 glass available fromSchott North America, Inc. of Elmsford, N.Y., can be used.

Difunctional organo-metalic and/or silanes, as well as otherpolyorgano-metalic and/or silanes, can be used in the surface-coatingprotocol and can be disposed on the surface at a level not to exceed theamount required to form a two dimensional networked monolayer oforgano-metalic and/or silane groups on the surface. In some embodiments,it is preferred that the level of organo-metalic and/or silane groupsdisposed on the surface not exceed the amount required to bond withevery hydroxyl group present on the surface, and thus not forming anetworked monolayer. If used as a 0.02 to about 0.06% by weight of anabout 4000 molecular weight difunctional organo-metalic and/or silane bytotal weight of a composition, a substrate can be dipped in thecomposition for about 30 seconds to about 5 minutes. In someembodiments, a disilane and/or diorgano-metalic can be used in the formof a 1/10% to 4.0% by weight solution for spray and spin application ofFLUOROSYL FSD4500, a perfluoropolyether with two ethoxysilane terminalgroups, available from Cytonix LLC of Beltsville, Md. In someembodiments, an approximately 2000 molecular weight disilane may be usedwith adjustments in laydown according to the molecular weight, forexample, Solvay FLUOROLINK® S10, a perfluoropolyether with twoethoxysilane terminal groups, available from Solvay Solexis, Inc. ofWest Deptford, N.J. The quantity of organo-metalic and/or silane to forma monolayer is approximately proportional to its molecular weights.Using a significant excess of organo-metalic and/or silanes cancompromise abrasion resistance, oleophobicity, and hydrophobicity, asexposed organo-metalic and/or silane or hydrolyzed groups may be presentat the exposed surface. Exposed hydroxyl groups at the surfacecontribute to wettability and friction. Instead, a relativelystoichiometric amount of organo-metalic and/or silane relative to theamount of hydroxyl groups and free surface area, is used. A PFPEdisilane, a trisilane, a tetrasilane, and silane molecules with highernumbers of silane or organo-metalic groups can be used, as can PFPEmolecules with still larger numbers of silane or organo-metalic groups.A polysilane or a different polyorgano-metalic molecule may have silaneor organo-metalic groups located at one end of the molecule, at bothends of the molecule, or distributed in any way. In some embodiments,dipodal organo-metalic and/or silanes are preferred. Polysilanes andother polyorgano-metalics may have pendant groups that are organic,fluorinated, inorganic, functional, or combinations thereof. Uponapplication to the treated surface, the hydrolysable group, for examplean alkoxy or a halogen group, can hydrolyze releasing an alcohol orhalogen acid, which may come off in the air. SiOH then condenses andSiOSi is formed on the surface. In some cases the disilanes, FLUOROSYLFSD1500, FLUOROSYL FSD2500 or FLUOROSYL FSD4500, available from CytonixLLC of Beltsville, Md., can be used. In some embodiments a tetrasilanemay be used, such as FSQ3000 from Cytonix LLC of Beltsville, Md. Foroptimum hydrophobic and wear resistance, organo-metalics and/or silaneshaving a functionality of greater than one require that a relativelystoichiometric amount of organo-metalic and/or silane relative to theamount of hydroxyl groups and/or free surface area be used.

For a spray application of the polyorgano-metalic and/or silanecompositions, there are at least three factors that can be considered.These three factors are rate of delivery, belt speed/pan rate, andconcentration. In some embodiments of the present teachings, solventswith boiling points greater than 90° C. to greater than 150° C. may beused, and fluorinated oils may be used which are not volatile. Thecoated surface can be tested for water contact angle, water contactangle, roll-off (slip) angle, and abrasion resistance. Various surfaceanalysis techniques can be used, for example, those described by Liu etal., slip angle testing, x-ray techniques, and laser techniquesinvolving burning off a layer and testing by chromatography. An abrasiontest can use materials such as but not limited to cotton, rubber,leather, sand paper, abrasives or steel wool rubbed repeatedly at apressure of about 1 pound per square inch or higher against the treatedsurface. A contact angle of about 110° or greater for water isdesirable. After, for example the steel wool application, the watercontact angle should remain at least about 100°. According to variousembodiments of the present teachings, touch screens are provided thatexhibit a water contact angle of at or above 100° after 6000 rubs with0000 steel wool at 1 pound per square inch pressure and 3000 rubs at 2.5grams per square millimeter. In other tests measuring the retention ofstains from liquids commonly found in homes and offices, it is desirableto have no visible retention.

Depending on the type of organo-metalics and/or silanes used, across-linker or bridging agent can be used to bring together isolatedorgano-metalic and/or silane molecules into two-dimension networks ofinterconnected organo-metalic and/or silanes bonded to the surface ofthe treated substrate by all available hydroxyl groups exposed on thesubstrate surface. Examples of cross-linkers and bridging agents includemetals and metal oxides, organo-metalic compounds, tetraalkoxysilanes,dipodal organo-metalic and/or silanes, disilanes, tetrasilanes, orcombinations thereof. In some embodiments of the present teachings,organo-metalic compounds may be used individually or in combination,which include those comprising vanadium, aluminum, titanium, zirconium,tin, and others well known in the art. In some embodiments, about 1% byweight to about 8% by weight tetraalkoxysilane may be used, based on the4500 molecular weight of FLUOROSYL FSD 4500 molecules, aperfluoropolyether disilane available from Cytonix LLC of Beltsville,Md. It is preferred that there be a molar equivalent of water presentequal to or greater than the molar weight of silol on the disilaneand/or other silanes and other organo-metalic compounds which might bepresent. The concentration of organo-metalic and/or silane for applyingin a formulation comprising a fluorosolvent or fluorochlorosolvent canbe from about 0.001% to about 4% depending on the application processand conditions. Alcohol can be added with water, acids,tetraalkoxysilanes, alkoxyorgano-metalics, or other organic componentsto promote solubility in the fluorinated solvent. An acid or base may beused to catalyze the hydrolyzation step and promote silol formation.Anhydrides and other catalysts are known to promote silol formation.Examples of solvents that can be used include dichloropentafluoropropane(FREON 225), available from E.I. duPont deNemours (DuPont) ofWilmington, Del., ASAHIKLIN AK-225, available from Asahi Glass Co., Ltd.of Tokyo, Japan, and VERTREL® MCA, available from DuPont. In someembodiments, a solvent blend is used that includes a fluorinatedsolvent, 8.0% by weight alcohol and 0.5% by weight acid based on thetotal weight of the solvent blend. Examples of acids include 3.0% HCl byweight of the total weight of an acid solution, citric acid, and vinegar(acetic acid).

According to various embodiments of the present teachings, the silylethers of pendant perfluoropolyethers are particularly preferred. Thecoating composition can comprise a first reaction product of a vinylether functionalized pendent, as opposed to a linear, perfluoropolyether(PFPE), and a second reactant comprising a trichloro-silane, forexample, a pendant perfluoropolyether trichlorosilane. In someembodiments the coating composition can comprise a reaction product ofthe first reaction product, for example, a second, subsequent reactionproduct of the first reaction product and a third reactant comprising atleast one of trimethylortoformamate, triethylorthoformamate,tripropylorthoformamate, or a triarylorthoformamate.

Exemplary pendent PFPEs, second reactants, first reaction products,third reactants, fourth reactants, and second reaction products that canbe used and formed include those shown in the reaction scheme below:

wherein n is from about 3 to about 30 or larger. In some embodiments, nin any of the formulae above can instead be from about 3 to about 25,from about 4 to about 20, from about 5 to about 20, or from about 10 toabout 20. Methylorthoformamate, shown in the above example, can besubstituted by any alkylorthoformamate or arylorthoformamate.Perfluoropolyether polysilanes, for example perfluoropolyetherdisilanes, can be formed according to the reaction scheme illustratedabove, and other reaction schemes are known in the art for forming thefirst, second and polysilane reaction products. Methods that includecarrying out the reactions according to one or more of these schemes areincluded in the present teachings. The present teachings also relate tomethods that include coating substrates and forming such coatingcompositions on substrates. Exemplary pendant perfluoropolyethers thatcan be used in the first reaction scheme include KRYTOX, a PFPE-Kavailable from DuPont de Nemours, of Wilmington, Del., and Fomblin-Y, aPFPE-Y available from Solvay Solexis, Inc., West Deptford, N.J. In someembodiments, the second of these two reaction schemes is used butwherein the methoxy group (OCH₃) shown in the second reactant caninstead be an alkoxy group, an aryloxy group, for example ethoxy orphenoxy, or a combination thereof. Exemplary precursors for formingdi-functional perfluoropolyethers that can be used in the first reactionscheme to produce disilanes are FluoroLink D10, Fluorolink D10H,Fluorolink D, and FluoroLink D4000, and an exemplary precursor forforming a tetra-function perfluoropolyether that can be used in thefirst reaction scheme to produce a tetrasilane available from SolvaySolexis, Inc., West Deptford, N.J. Compositions of the present teachingscan comprise a wide range of additives and co-agents, including but notlimited to, nano-sized and micro-sized objects of all shapes andproperties, such as particles, fibers, nano-tubes and other natural,manufactured and engineered components, said objects can have dimensionswhich are smaller than the wavelengths of visible, ultraviolet andinfrared light or selected ranges therein. In some embodiments, one ormore of said objects may comprise a volume which is greater or less thanthe total volume of the composition, substantially greater than thetotal volume, and may be present at or on the surface of coatingscomprising the composition. In some embodiments, the composition maycomprise non-volatile fluids, for example, fluorinated fluids, which canbe present in the composition, dispersed in the composition, at thesurface of the composition, or combinations thereof. In someembodiments, the composition can comprise solvents, such a fluorinatedand/or halogenated solvents, initiators, catalysts, resins, reactantshaving more than one reactive functionality, monomers, polymers, organicand inorganic substances. In some embodiments, the composition itselfcan be formed into articles, films, powders, and objects as describedherein. In some embodiments, the surface of the composition can beformed to have a continuous or discontinuous, repeating or randomtopography, shape, relief, impression, texture, a roughness, pattern,design, feature, a height to width aspect ratio of a feature, a volumeof a feature, or combinations thereof. In some embodiments, surfacesformed by or of the composition can be superhydrophobic, with contactangles to water that are greater than about 120 degrees to greater thanabout 170 degrees. In some embodiments, surfaces formed by or of thecomposition can be exceptionally resistant to adhesion by stains, marks,snow, ice, organic oils, common household and industrial substances, andpollutants. In some embodiments, surfaces formed by or of thecomposition can be exceptionally slippery, lubricious, and have anexceptionally low coefficient of friction. Touch screens can be coatedwith such coating compositions, and other articles, including thosehaving various and substantially different properties and uses, can alsobenefit from such coatings, for example, smooth, rough, patterned,lithographed, micro and/or nano featured, superhydrophobic, textured,designed, printed, imprinted, porous, tubular, sintered, striated,reliefed, impressioned, hollowed, foamed edged, powdered, powder-coated,etched, selectively-located, embossed, woven, non-woven, molded orformed surfaces, lotus-effect surfaces, electrowetting surfaces,laboratory vessels, fluidic devices, medical devices, powders, fibers,optical fibers, optical or electrical components, signal transmitters,signal receivers, signal reflectors, radomes, vehicular surfaces,architectural surfaces, outdoor furniture, household goods, kitchenarticles, kitchen surfaces, bathroom articles, bathroom surfaces,antennae, microwave antennae, dishes, reflectors, signs, visualsignaling devices, scanner windows, lenses, liquid crystal displays,electrowetting displays, 3D displays, and video displays.

In some embodiments, the composition comprises the reaction productobtained after a substantially complete condensation reaction ofcomponents A and B, wherein: component A comprises at least one of apendent perfluoropolyether trichloro-silane shown in the first reaction,a pendent perfluoropolyether aryloxy-silane shown in the first reactionscheme below, scheme below, or a pendent perfluoropolyether alkoxysilaneshown in the second reaction scheme below

wherein n is from 3 to about 30; and component B comprises atetraalkoxysilane in an amount of 8% by weight or less based on thetotal weight of components A and B combined together. Component B can bea tetraalkoxysilane present in an amount of from about 1% by weight toabout 7% by weight, or from about 2% by weight to about 6% by weightbased on the total weight of components A and B combined together.Component B can comprise organo-metalic compounds, metals, metalcompounds, organic compounds, inorganic compounds, or any combinationthereof, and Component B may be present in an amount greater than about10% by weight of the total weight of components A and B. For example,Component B may be present in the applied coating at from about 1% byweight to about 99% by weight of the total weight of components A and B.In some embodiments Component A can be applied without Component B, or,in other embodiments, Component B may be applied a substantial period oftime before the application of Component A. Component A can have anumber average molecular weight of from about 500 to about 10,000, orfrom about 1,000 to about 5,000, or from about 2,000 to about 4,500. Acoated substrate is also provided wherein the coating composition iscoated on a surface of the substrate and the coating has a thickness offrom about 2 nanometers (nm) to about 4 nm, from about 1 nm to about 5nm, or of less than 2 nm. The coating can comprise a mono-molecularlayer of the reaction product and the monomolecular layer can becontinuous with the underlying substrate so as to constitute amonolithic surface comprising exposed fluorine compounds. In someembodiments, component B forms a continuous, substantially condensedlayer on the underlying substrate that can be from about 1 monolayer inthickness (<1 nanometer) to about 100 nm or more, and component A formsa substantially homogeneous, condensed, continuous monolayer oncomponent B so as to constitute a monolithic surface comprising exposedfluorine compounds. Component B can further comprise an organo-metaliccomponent or other suitable component known in the art, such as anorgano-metalic compound. In some embodiments throughout the presentteaching, Component A may be applied by any means without the presenceof a Component B to from a continuous, substantially condensed layer onthe underlying substrate, where a fraction of the molecules of thecomposition are bound to the underlying substrate surface and toadjacent molecules, and the remaining fraction are bound only toadjacent molecules, functioning as cross-linking or bridging agents.Compositions of the present teachings can comprise a wide range ofadditives and co-agents, including but not limited to, nano-sized andmicro-sized objects of all shapes and properties, such as particles,fibers, nano-tubes and other natural, manufactured and engineeredcomponents, said objects can have dimensions which are smaller than thewavelengths of visible, ultraviolet and infrared light or selectedranges therein. In some embodiments, one or more of said objects maycomprise a volume which is greater or less than the total volume of thecomposition, substantially greater than the total volume, and may bepresent at or on the surface of coatings comprising the composition. Insome embodiments, the composition can comprise non-volatile fluids, forexample, fluorinated fluids, which can be present in the composition,dispersed in the composition, at the surface of the composition, orcombinations thereof. In some embodiments, the composition can comprisesolvents, such a fluorinated and/or halogenated solvents, initiators,catalysts, resins, reactants having more than one reactivefunctionality, monomers, polymers, organic and inorganic substances. Insome embodiments, the composition itself can be formed into articles,films, powders, and objects as described herein. In some embodiments,the surface of the composition can be formed to have a continuous ordiscontinuous, repeating or random topography, shape, relief,impression, texture, a roughness, pattern, design, feature, a height towidth aspect ratio of a feature, a volume of a feature, or combinationsthereof. In some embodiments, surfaces formed by or of the compositioncan be superhydrophobic, with contact angles to water that are greaterthan about 120 degrees to greater than about 170 degrees. In someembodiments, surfaces formed by or of the composition can beexceptionally resistant to adhesion by stains, marks, snow, ice, organicoils, common household and industrial substances, and pollutants. Insome embodiments, surfaces formed by or of the composition can beexceptionally slippery, lubricious, and have an exceptionally lowcoefficient of friction. In some cases a touch screen device is providedcomprising a touch screen and a coating on the touch screen, wherein thecoating comprises the composition. In some cases a 3D imaging device isprovided comprising a screen and a coating on the screen, wherein thecoating comprises the composition. In some cases an electrowettingdisplay device is provided comprising a screen and a coating on thescreen. In some cases a touch screen, a 3D imaging device, and anelectrowetting display device may be present in a display device. Moregenerally, any article can be coated with the composition, for example,smooth, rough, patterned, lithographed, micro and/or nano featured,superhydrophobic, textured, designed, printed, imprinted, porous,tubular, sintered, striated, reliefed, impressioned, hollowed, foamed,edged, powdered, powder-coated, etched, selectively-located, embossed,woven, non-woven, molded or formed surfaces, lotus-effect surfaces,electrowetting surfaces, laboratory vessels, fluidic devices, medicaldevices, powders, fibers, optical fibers, optical or electricalcomponents, signal transmitters, signal receivers, signal reflectors,radomes, vehicular surfaces, architectural surfaces, outdoor furniture,household goods, kitchen articles, kitchen surfaces, bathroom articles,bathroom surfaces, antennae, microwave antennae, dishes, reflectors,signs, visual signaling devices, scanner windows, lenses, liquid crystaldisplays, electrowetting displays, 3D displays, and video displays. Inaddition, the present invention relates to processes of coating smallarticle surfaces, for example, smart phone touch screens, tabletcomputer screens, and the like, with nominal solvent loss.

In yet other embodiments of the present teachings, a composition isprovided that comprises at least one pendent perfluoropolyethertrichloro-silane of the formula

wherein n is from 3 to about 30. The pendent perfluoropolyether cancomprise, for example, a PFPE-K or a PFPE-Y. The composition can furthercomprise a solvent comprising a fluorinated solvent. Compositions of thepresent teachings can comprise a wide range of additives and co-agents,including but not limited to, nano-sized and micro-sized objects of allshapes and properties, such as particles, fibers, nano-tubes and othernatural, manufactured and engineered components, said objects can havedimensions which are smaller than the wavelengths of visible,ultraviolet and infrared light or selected ranges therein. In someembodiments, one or more of said objects may comprise a volume which isgreater or less than the total volume of the composition, substantiallygreater than the total volume, and may be present at or on the surfaceof coatings comprising the composition. In some embodiments, thecomposition can comprise non-volatile fluids, for example, fluorinatedfluids, which can be present in the composition, dispersed in thecomposition, at the surface of the composition, or combinations thereof.In some embodiments, the composition can comprise solvents, such afluorinated and/or halogenated solvents, initiators, catalysts, resins,reactants having more than one reactive functionality, monomers,polymers, organic and inorganic substances. In some embodiments, thecomposition itself can be formed into articles, films, powders, andobjects as described herein. In some embodiments, the surface of thecomposition can be formed to have a continuous or discontinuous,repeating or random topography, shape, relief, impression, texture, aroughness, pattern, design, feature, a height to width aspect ratio of afeature, a volume of a feature, or combinations thereof. In someembodiments, surfaces formed by or of the composition can besuperhydrophobic, with contact angles to water that are greater thanabout 120 degrees to greater than about 170 degrees. In someembodiments, surfaces formed by or of the composition can beexceptionally resistant to adhesion by stains, marks, snow, ice, organicoils, common household and industrial substances, and pollutants. Insome embodiments, surfaces formed by or of the composition can beexceptionally slippery, lubricious, and have an exceptionally lowcoefficient of friction. In some cases a touch screen device is providedcomprising a touch screen and a coating on the touch screen, wherein thecoating comprises the composition. In some cases a 3D imaging device isprovided comprising a screen and a coating on the screen, wherein thecoating comprises the composition. In some cases an electrowettingdisplay device is provided comprising a screen and a coating on thescreen. More generally, any article can be coated with the composition,for example, smooth, rough, patterned, lithographed, micro and/or nanofeatured, superhydrophobic, textured, designed, printed, imprinted,porous, tubular, sintered, striated, reliefed, impressioned, hollowed,foamed, edged, powdered, powder-coated, etched, selectively-located,embossed, woven, non-woven, molded or formed surfaces, lotus-effectsurfaces, electrowetting surfaces, laboratory vessels, fluidic devices,medical devices, powders, fibers, optical fibers, optical or electricalcomponents, signal transmitters, signal receivers, signal reflectors,radomes, vehicular surfaces, architectural surfaces, outdoor furniture,household goods, kitchen articles, kitchen surfaces, bathroom articles,bathroom surfaces, antennae, microwave antennae, dishes, reflectors,signs, visual signaling devices, scanner windows, lenses, liquid crystaldisplays, electrowetting displays, 3D displays, and video displays.

In some embodiments a composition is provided that comprises at leastone pendent perfluoropolyether alkoxysilane of the formula

wherein n is from 3 to about 30. The pendent perfluoropolyether cancomprise, for example, a PFPE-K or a PFPE-Y. The composition can furthercomprise a solvent comprising a fluorinated solvent. Compositions of thepresent teachings can comprise a wide range of additives and co-agents,including but not limited to, nano-sized and micro-sized objects of allshapes and properties, such as particles, fibers, nano-tubes and othernatural, manufactured and engineered components, said objects can havedimensions which are smaller than the wavelengths of visible,ultraviolet and infrared light or selected ranges therein. In someembodiments, one or more of said objects may comprise a volume which isgreater or less than the total volume of the composition, substantiallygreater than the total volume, and may be present at or on the surfaceof coatings comprising the composition. In some embodiments, thecomposition can comprise non-volatile fluids, for example, fluorinatedfluids, which can be present in the composition, dispersed in thecomposition, at the surface of the composition, or combinations thereof.In some embodiments, the composition can comprise solvents, such afluorinated and/or halogenated solvents, initiators, catalysts, resins,reactants having more than one reactive functionality, monomers,polymers, organic and inorganic substances. In some embodiments, thecomposition itself can be formed into articles, films, powders, andobjects as described herein. In some embodiments, the surface of thecomposition can be formed to have a continuous or discontinuous,repeating or random topography, shape, relief, impression, texture, aroughness, pattern, design, feature, a height to width aspect ratio of afeature, a volume of a feature, or combinations thereof. In someembodiments, surfaces formed by or of the composition can besuperhydrophobic, with contact angles to water that are greater thanabout 120 degrees to greater than about 170 degrees. In someembodiments, surfaces formed by or of the composition can beexceptionally resistant to adhesion by stains, marks, snow, ice, organicoils, common household and industrial substances, and pollutants. Insome embodiments, surfaces formed by or of the composition can beexceptionally slippery, lubricious, and have an exceptionally lowcoefficient of friction. In some cases a touch screen device is providedcomprising a touch screen and a coating on the touch screen, wherein thecoating comprises the composition. In some cases a 3D imaging device isprovided comprising a screen and a coating on the screen, wherein thecoating comprises the composition. In some cases an electrowettingdisplay device is provided comprising a screen and a coating on thescreen. More generally, any article can be coated with the composition,for example, smooth, rough, patterned, lithographed, micro and/or nanofeatured, superhydrophobic, textured, designed, printed, imprinted,porous, tubular, sintered, striated, reliefed, impressioned, hollowed,foamed edged, powdered, powder-coated, etched, selectively-located,embossed, woven, non-woven, molded or formed surfaces, lotus-effectsurfaces, electrowetting surfaces, laboratory vessels, fluidic devices,medical devices, powders, fibers, optical fibers, optical or electricalcomponents, signal transmitters, signal receivers, signal reflectors,radomes, vehicular surfaces, architectural surfaces, outdoor furniture,household goods, kitchen articles, kitchen surfaces, bathroom articles,bathroom surfaces, antennae, microwave antennae, dishes, reflectors,signs, visual signaling devices, scanner windows, lenses, liquid crystaldisplays, electrowetting displays, 3D displays, and video displays.

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

While embodiments of the present disclosure have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the disclosure. It should beunderstood that various alternatives to the embodiments of thedisclosure described herein may be employed in practicing thedisclosure. The alternative embodiments disclosed in various paragraphsand sections of the disclosure should be construed to apply, whereappropriate, in all paragraphs and sections of the disclosure. It isintended that the following claims define the scope of the disclosureand that methods and structures within the scope of these claims andtheir equivalents be covered thereby.

What is claimed is:
 1. A micro-sized or nano-sized object coated with aperfluoropolyether silane composition consisting of a perfluoropolyethersilane and optionally a non-volatile fluorinated oil, theperfluoropolyether silane having the formula: R_(f)—CH₂—O_(w)—R—Si(Y)₃wherein R_(f) represents a K type perfluoropolyether or a Y typeperfluoropolyether, Y represents a hydrolysable group independentlyselected from a chloro group, an alkoxy group, an acyloxy group, and anaryloxy group, R represents an alkyl group of 1 to 4 carbon atoms, and wis 0 or
 1. 2. The micro-sized or nano-sized object of claim 1, whereinthe object is a powder or a fiber.
 3. A coating comprising themicro-sized or nano-sized object of claim 1, wherein the object is inthe coating, at a surface of the coating, or both.
 4. The micro-sized ornano-sized object of claim 1, wherein the perfluoropolyether silanecomposition consists of the perfluoropolyether silane and thenon-volatile fluorinated oil.
 5. An article comprising a rough surfacethat is coated, at least in part, by a coating composition comprisingthe micro-sized or nano-sized object of claim 1, wherein the roughsurface has a repeating or random topography, a relief, an impression, atexture, a pattern, a design, a feature, or a combination thereof.
 6. Anarticle comprising a rough surface that is coated, at least in part, bya coating composition comprising the micro-sized or nano-sized object ofclaim 1, wherein the rough surface has a pattern.
 7. A surfacecomprising the coating of claim 3, wherein the surface exhibits acontact angle to water of 170° or greater.
 8. A micro-sized ornano-sized object coated with a perfluoropolyether silane compositionconsisting of a perfluoropolyether silane and optionally a non-volatilefluorinated oil, the perfluoropolyether silane having the formula:R_(f)—CH₂—R—Si(Y)₃ wherein R_(f) represents a K type perfluoropolyetheror a Y type perfluoropolyether, Y represents a hydrolysable groupindependently selected from a chloro group, an alkoxy group, an acyloxygroup, and an aryloxy group, and R represents an alkyl group of 1 to 4carbon atoms.
 9. The micro-sized or nano-sized object of claim 8,wherein the object is a powder or a fiber.
 10. A coating comprising themicro-sized or nano-sized object of claim 8, wherein the object is inthe coating, on a surface of the coating, or both.
 11. The micro-sizedor nano-sized object of claim 8, wherein the perfluoropolyether silanecomposition consists of the perfluoropolyether silane and thenon-volatile fluorinated oil.
 12. An article comprising a rough surfacethat is coated, at least in part, by a coating composition comprisingthe micro-sized or nano-sized object of claim 8, wherein the roughsurface has a repeating or random topography, a relief, an impression, atexture, a pattern, a design, a feature, or a combination thereof. 13.An article comprising a rough surface that is coated, at least in part,by a coating composition comprising the micro-sized or nano-sized objectof claim 8, wherein the rough surface has a pattern.
 14. A surfacecomprising the coating of claim 10, wherein the surface exhibits acontact angle to water of 170° or greater.
 15. A micro-sized ornano-sized object coated with a perfluoropolyether silane compositionconsisting of a perfluoropolyether silane and a non-volatile fluorinatedoil, the perfluoropolyether silane having the formula:R_(f)—CH₂—O—R—Si(Y)₃ wherein R_(f) represents a K typeperfluoropolyether or a Y type perfluoropolyether, Y represents ahydrolysable group independently selected from a chloro group, an alkoxygroup, an acyloxy group, and an aryloxy group, and R represents an alkylgroup of 1 to 4 carbon atoms.
 16. The micro-sized or nano-sized objectof claim 15, wherein the object is a powder or a fiber.
 17. A coatingcomprising the micro-sized or nano-sized object of claim 15, wherein theobject is in the coating, at a surface of the coating, or both.
 18. Anarticle comprising a rough surface that is coated, at least in part, bya coating composition comprising the micro-sized or nano-sized object ofclaim 15, wherein the rough surface has a repeating or randomtopography, a relief, an impression, a texture, a pattern, a design, afeature, or a combination thereof.
 19. An article comprising a roughsurface that is coated, at least in part, by a coating compositioncomprising the micro-sized or nano-sized object of claim 15, wherein therough surface has a pattern.
 20. A surface comprising the coating ofclaim 17, wherein the surface exhibits a contact angle to water of 170°or greater.